Theoretical insights of copper(I)-nitrene complexes

Density functional theory has been used to study the geometries and character of the copper-nitrene complexes LnCuNR (1, R = Me; 2, R = CO2Me; 3, R = SO2Me; 4, R = SO2ph). Calculation results confirm that the copper-nitrene nitrogen bonds of the copper-nitrene complexes A2, B2, C2, and D2 (R=CO2Me) show strong double-bonded character, and thus those of the copper-nitrene complexes A1, A3, A4, B1, B3, B4, C1, C3, C4, D1, D3, D4, E1, E2, E3, E4, F1, F2, F3, and F4 show single-bonded character. The copper-nitrene nitrogen bonds and the copper and nitrogen atoms of the bonds are the reactive center for the copper-nitrene complexes. The geometry, electronic structure, frontier orbitals (HOMO and LUMO), and molecular electrostatic potential (MEP) are discussed in detail.